CN108067252A - A kind of noble metal hydrogenation desulphurization catalyst and its preparation method and application - Google Patents
A kind of noble metal hydrogenation desulphurization catalyst and its preparation method and application Download PDFInfo
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- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
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Abstract
The invention belongs to Hydrobon catalyst technical fields, and in particular to a kind of noble metal hydrogenation desulphurization catalyst and its preparation method and application.The catalyst includes carrier and noble metal active component, and the presoma of the carrier is houghite containing cobalt, and the noble metal component is distributed in the surface of houghite containing cobalt with simple substance form.In the preparation process of the catalyst, noble metal active component loading process reduces fixed precious metal simple substance using autoreduction mode, that is, utilizes Co in houghite2+Reproducibility and precious metal salt (PtCl4 2‑,PdCl4 2‑) oxidisability achieve the purpose that reduce noble metal, being compared than traditional infusion process has better dispersion effect, and it is preferably fixed on carrier surface, and after high-temperature roasting, catalyst surface is uniformly distributed oxidation state active site.
Description
Technical field
The invention belongs to Hydrobon catalyst technical fields, and in particular to a kind of noble metal hydrogenation desulphurization catalyst and its
Preparation method and application.
Background technology
It is well known that increasingly deficient, the heaviness of crude oil and in poor quality day in world wide with world energy sources resource
Become serious.At the same time, Law on Environmental Protection is increasingly strict, develops high performance with deep hydrodesulfurizationof (HDS) catalyst
Have become the hot spot in current hydrofinishing field.For the sulfur-containing compound in petrol and diesel oil, it is more difficult de- to include some
The organic sulfur compound removed, such as thiophene and alkyl-substituted dibenzothiophenes, in traditional CoMo/Al2O3Hydrobon catalyst
The upper removing that can reach small molecule sulphur by direct desulfurization (DDS) path, but have for the macromolecular of these more difficult removings
Machine sulfide, such as 4,6- dimethyl Dibenzothiophenes (4,6-DMDBT), the space bit caused by being introduced due to the methyl of 4 and 6
Resistance, is difficult directly to remove by DDS paths, and can only could realize preferable desulfurization effect by being hydrogenated with path, therefore, is developed
Key with depth H DS catalyst is to improve the hydrogenation capability of catalyst.
Traditional Hydrobon catalyst is mainly CoMo bases catalyst and the phosphide developed later, nitride and
Carbide Hydrobon catalyst, cheap although these catalyst preparations are simple, the effect in terms of deep desulfuration is simultaneously
It is undesirable.Therefore the noble metal catalyst with aromatic hydrogenation ability attracts people's attention, and research emphasis focuses primarily on
Improve the sulfur resistance and anti-sintering property of noble metal catalyst.Improving the sulfur resistive and anti-sintering property of noble metal catalyst
In, the effect of carrier is the most apparent, and the interaction between carrier and noble metal is to influence the principal element of catalytic effect, therefore is needed
Want such a high performance carrier.At present, the noble metal hydrogenation desulfurization catalyst agent carrier studied has γ-Al2O3, SiO2,
The carriers such as Si-MCM-41 and Al-MCM-41 and some other molecular sieves and oxide catalyst, also have some to study people
Member is by improving these support modifications the hydrodesulfurization effect of catalyst.Although above-mentioned catalyst have certain activity and
Sulfur tolerance, but in high-temperature reaction process the noble metal of catalyst surface easily occur reunite stability is caused to reduce, and be catalyzed
Traditional infusion process is used in the preparation process of agent, active component dispersion effect is general.
To solve the problems, such as that catalyst activity component is easily reunited, Chinese patent literature CN102407121B is disclosed
It is a kind of using X/Ni/Al houghites as the preparation method of the hydrogenation catalyst of presoma, be prepared into first by coprecipitation method
To the X/Ni/Al houghites with layer structure, then the X/Ni/Al houghites of layer structure are placed in Muffle furnace and are roasted
It burns, obtains the metal composite oxide containing X/Ni/Al, last hydrogenated metal composite oxide of the reduction containing X/Ni/Al obtains
Hydrogenation catalyst containing X/Ni/Al.The catalyst thermal stability that is prepared by this patent document is good, reactivity is high,
It is cheap and with well recycling effect.But it is not a kind of Hydrobon catalyst, and uses co-precipitation side
The houghite catalyst that method is prepared, non-uniform defect is disperseed there are active metal component in the carrier.
The content of the invention
Therefore, the technical problem to be solved in the present invention is in the active metal in Hydrobon catalyst in the prior art is overcome
Component is unevenly distributed, thermal stability is poor, easy-sintering, it is poor to the organic sulfur compound removal effect of macromolecular the defects of, so as to carry
For a kind of noble metal hydrogenation desulphurization catalyst and its preparation method and application.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：
A kind of noble metal hydrogenation desulphurization catalyst, including carrier and noble metal active component, the presoma of the carrier is
Houghite containing cobalt, the noble metal component are distributed in the surface of houghite containing cobalt with oxidation states.
Preferably, the houghite containing cobalt is cobalt aluminium houghite or cobalt magnesia-alumina hydrotalcite.
Preferably, the noble metal active component is platinum or palladium.
Preferably, the noble metal active component accounts for noble metal hydrogenation desulphurization catalyst according to the quality meter of its simple substance
0.5-6%.
A kind of preparation method of above-mentioned noble metal hydrogenation desulphurization catalyst, comprises the following steps：
(1) using conventional method, by aging, centrifuge, be dried to obtain houghite containing cobalt；
(2) cobalt houghite will be contained to be dispersed in water, and the slurries of houghite containing cobalt will be obtained, by the salting liquid of noble metal and its
6-18h is stirred in mixing, is stood, and is filtered, and is washed, dry；After autoreduction mode reduces noble metal, then roast and aoxidized
State Hydrobon catalyst；
(3) step (2) products obtained therefrom is roasted, calcination temperature is 400-600 DEG C, and roasting time 2-4h obtains institute
State noble metal hydrogenation desulphurization catalyst.
Preferably, the salting liquid of the noble metal be chloroplatinate solution or chloropalladate solution, preferred chloroplatinate
Solution is Na2PtCl4Or K2PtCl4Solution, preferred chloropalladate solution are Na2PdCl4Or K2PdCl4Solution.
Preferably, the concentration of the salting liquid of the noble metal is 0.05-0.15mol/l.
Preferably, the heating rate of calcination steps is 3-6 DEG C/min.
Preferably, houghite containing cobalt is prepared using coprecipitation or hydro-thermal method.
Wherein, the autoreduction disperses to be to utilize Co in houghite2+Reproducibility and precious metal salt oxidisability will
Precious metal ion, which is reduced to simple substance, to be disperseed and is fixed on carrier surface.
A kind of above-mentioned noble metal hydrogenation desulphurization catalyst answering in the reaction of macromolecular organic sulfur compound in feedstock oil is removed
With.
Further, the macromolecular organic sulfur compound is thiophene, benzothiophene, dibenzothiophenes, 2,5- dimethyl thiophenes
Fen or 4,6- dimethyl Dibenzothiophenes etc..
N-heptane solution using thiophene or 4,6- dimethyl Dibenzothiophenes (4,6-DMDBT) content as 1-5wt% is mould
Type raw materials of compound.Rhohene desulfiirization reacts：0.1-5g catalyst is packed into hydrodesulfurization unit, first at 300 DEG C, uses hydrogen
(30-80ml/min) is to oxidized catalyst presoma reductase 12 h.Switching reaction, reaction condition are after the completion of reduction：Normal pressure,
280-400 DEG C, hydrogen flowing quantity is 90-200ml min-1.Then pure hydrogen is satisfied by the chemical industry containing organic sulfur at 18 DEG C of constant temperature
And device.After reaction, analysis test is carried out using GC.
4,6- dimethyl Dibenzothiophene desulphurization reactions：1-5ml catalyst is packed into hydrodesulfurization unit, is existed first
300 DEG C, with hydrogen (30-80ml/min) to oxidized catalyst presoma reductase 12 h.Switching reaction after the completion of reduction, reacts item
Part is：Normal pressure, 280-400 DEG C, hydrogen to oil volume ratio 100-500, liquid hourly space velocity (LHSV) 0.5-2.5h-1, when reaction time 8-24 is small.
After reaction, analysis test is carried out using sulphur blood urea/nitrogen analyzer, the conversion ratio expression of activity thiophene or 4,6-DMDBT are stablized
Property test also carry out on the apparatus.
Prepared by the coprecipitation of houghite containing cobalt or hydro-thermal method, coprecipitation is with NaOH and Na2CO3For precipitation
Agent, cobalt salt, magnesium salts, aluminium salt selection Co (NO3)2·6H2O、Mg(NO3)2·6H2O、Al(NO3)3·9H2O or corresponding sulfate
Or chlorate.
Hydro-thermal method is using urea as precipitating reagent, cobalt salt, magnesium salts and aluminium salt selection Co (NO3)2·6H2O、Mg(NO3)2·6H2O、
Al(NO3)3·9H2O or corresponding sulfate and chlorate.
The autoreduction mode is to mix houghite with precious metal salt, is stirred, and is stood.Using in houghite
Co2+Reproducibility and precious metal salt (PtCl4 2-,PdCl4 2-) oxidisability achieve the purpose that the scattered noble metal of reduction.
The preparation method of the houghite containing cobalt includes the following steps：
(1) coprecipitation (CP) synthesizes：The mixed solution of a certain concentration metal cation salt is slowly dripped by peristaltic pump
Enter in uniformly mixed certain density precipitating reagent, 80-100 DEG C be warming up to after being added dropwise, then adjust pH=10 or so,
Continue to stand 12-36h after stirring 2-4h, centrifuge, wash to pH=7,80-120 DEG C of dry 12-24h and obtain CoAl-LDHs afterwards
Or CoMgAl-LDHs.
(2) hydro-thermal method (HT) synthesizes：The mixed solution of a certain concentration metal cation salt is slowly dropped by peristaltic pump
It in uniformly mixed certain density urea liquid, waits to be added dropwise and is placed in water heating kettle, be subsequently placed in drying box
100-150 DEG C of holding 12-48h, gained suspension is centrifuged, wash afterwards after cooling to pH=7,80-120 DEG C of dry 12-36h
CoAl-LDHs or CoMgAl-LDHs is obtained afterwards.
In the preparation process of the houghite containing cobalt, metal cation salt is Co (NO3)2·6H2O、Mg(NO3)2·6H2O、
Al(NO3)3·9H2O or its corresponding sulfate, chlorate, precipitating reagent are NaOH and anhydrous Na2CO3, precipitating reagent is in hydro-thermal method
Urea.Wherein, metal cation salt Co (NO3)2·6H2O and Mg (NO3)2·6H2The substance of O amount and with Al (NO3)3·
9H2The ratio between amount of substance of O is 3：1-1：3.The substance withdrawl syndrome of NaOH is 0.32mol/L in precipitating reagent.Anhydrous Na2CO3's
The amount of substance and Al (NO3)3·9H2The amount of the substance of O is equal, and the substance withdrawl syndrome of urea liquid is preferably 0.5mol/L.
Technical solution of the present invention has the following advantages that：
1. heavy metal Hydrobon catalyst provided by the invention, using presoma of the houghite containing cobalt as carrier,
Noble metal active component is dispersed in the surface of houghite containing cobalt in the form of simple substance, noble metal active component in catalyst
Dispersed and anti-caking power improves, and hydrodesulfurization effect is good, enables in particular to the organic sulfur compound of effectively removing macromolecular.
2. the preparation method of noble metal hydrogenation desulphurization catalyst provided by the invention, noble metal active component loading process are adopted
Fixed precious metal simple substance is reduced with autoreduction mode, that is, utilizes Co in houghite2+Reproducibility and precious metal salt (PtCl4 2-,
PdCl4 2-) oxidisability achieve the purpose that reduce noble metal, than traditional infusion process compare have better dispersion effect, and will
It is preferably fixed on carrier surface, and after high-temperature roasting, catalyst surface is uniformly distributed oxidation state active site.
3. the preparation method of noble metal hydrogenation desulphurization catalyst provided by the invention, the houghite containing cobalt of preparation is using altogether
The precipitation method, it is simple for process that coprecipitation prepares hydrotalcite, easily operated, cheap, can be mass-produced, have it is wide should
Use prospect.
4. the application of noble metal hydrogenation desulphurization catalyst provided by the invention can be removed effectively in feedstock oil under normal pressure
Sulfide, the organic sulfur compound removal effect of especially macromolecular is apparent.
Specific embodiment
Embodiment 1
Coprecipitation prepares houghite containing cobalt：By 6.4015g NaOH and 1.9875g anhydrous Nas2CO3200ml is dissolved in go
In ionized water, poured into after stirring 20min in three-necked flask and continue to stir 1h, obtain precipitant solution；By cobalt magnesium and mole of aluminium
Than for 3:1 weighs 8.1852g Co (NO respectively3)2·6H2O, 7.2116g Mg (NO3)2·6H2O and 7.0331g Al (NO3)3·
9H2O is simultaneously dissolved in 200ml deionized waters, and the mixed solution of cobalt salt, magnesium salts and aluminium salt is obtained after being sufficiently stirred dissolving；Then use
The mixed solution of cobalt salt, magnesium salts and aluminium salt is slowly dropped into the speed of 6ml/min in precipitant solution and acutely stirred by peristaltic pump
It mixes, 60 DEG C is warming up to after being added dropwise, continue to be stirred to react 1h, stood for 24 hours after the completion of reaction, reaction solution is centrifuged, collected
Sediment is simultaneously washed to pH=7；Then in 100 DEG C of dry 12h, cobalt magnesia-alumina hydrotalcite CoMgAl-LDHs is obtained.
Then 1.0015g CoMgAl-LDHs are weighed to be dissolved in 200ml deionized waters, then are by 5ml substance withdrawl syndromes
5.64×10-2The Na of mol/l2PtCl4Solution is added in the above-mentioned suspension containing CoMgAl-LDHs and is vigorously stirred, in room
After the lower stirring 12h of temperature, obtained product is filtered, is first washed with deionized 3 times, is then washed 3 times with absolute ethyl alcohol again, it will
The product finally obtained is dried overnight in drying box in 100 DEG C, afterwards by dried catalyst in Muffle furnace, with 3 DEG C/
The rate of min is warming up to 600 DEG C of roasting 4h, obtains Pt/CoMgAl (CP) catalyst, is denoted as catalyst A.Catalyst A after testing
The mass fraction of middle Pd is 2.75%, through H2-O2The dispersion degree that titrimetry obtains Pt is 43.2%.
Embodiment 2
Coprecipitation prepares houghite containing cobalt：By 6.3978g NaOH and 2.6523g anhydrous Nas2CO3200ml is dissolved in go
In ionized water, poured into after stirring 20min in three-necked flask and continue to stir 1h, obtain precipitant solution；By the molar ratio of cobalt and aluminium
For 2:1 weighs 14.8745g Co (NO respectively3)2·6H2O and 9.3783g Al (NO3)3·9H2O is simultaneously dissolved in 200ml deionized waters
In, obtain cobalt salt and the mixed solution of aluminium salt after being sufficiently stirred dissolving；Then with peristaltic pump by cobalt salt and the mixed solution of aluminium salt
It is slowly dropped into precipitant solution and is vigorously stirred with the speed of 6ml/min, 60 DEG C are warming up to after being added dropwise, continue to stir
1h is reacted, is stood for 24 hours after the completion of reaction, reaction solution is centrifuged, sediment is collected and washs to pH=7；Then in 100 DEG C of dryings
12h obtains cobalt aluminium houghite CoAl-LDHs.
Then 1.0021g CoAl-LDHs are weighed to be dissolved in 200ml deionized waters, then are by 3.5ml substance withdrawl syndromes
11.28×10-2The Na of mol/l2PtCl4Solution is added in the above-mentioned suspension containing CoAl-LDHs and is vigorously stirred, in room temperature
After lower stirring 12h, obtained product is filtered, is first washed with deionized 3 times, then washed 3 times with absolute ethyl alcohol, obtained final
To product be dried overnight in drying box in 100 DEG C, afterwards by dried catalyst in Muffle furnace, with 5 DEG C/min's
Rate is warming up to 550 DEG C of roasting 3h, obtains Pt/CoAl (CP) catalyst, is denoted as catalyst B.The mass fraction of Pt in catalyst B
For 3.65%, through H2-O2The dispersion degree that titrimetry obtains Pt is 46.3%.
Embodiment 3
Coprecipitation prepares houghite containing cobalt：By 6.4017g NaOH and 3.1826g anhydrous Nas2CO3200ml is dissolved in go
In ionized water, poured into after stirring 20min in three-necked flask and continue to stir 1h, obtain precipitant solution；By the molar ratio of cobalt and aluminium
For 1:1 weighs 4.4624g Co (NO respectively3)2·6H2O and 5.6269g Al (NO3)3·9H2O is simultaneously dissolved in 200ml deionized waters
In, obtain cobalt salt and the mixed solution of aluminium salt after being sufficiently stirred dissolving；Then with peristaltic pump by cobalt salt and the mixed solution of aluminium salt
It is slowly dropped into precipitant solution and is vigorously stirred with the speed of 6ml/min, 60 DEG C are warming up to after being added dropwise, continue to stir
1h is reacted, is stood for 24 hours after the completion of reaction, reaction solution is centrifuged, sediment is collected and washs to pH=7；Then in 100 DEG C of dryings
12h obtains cobalt aluminum hydrotalcite CoAl-LDHs.
Then 0.9998g CoAl-LDHs are weighed to be dissolved in 200ml deionized waters, then are by 3.5ml substance withdrawl syndromes
5.64×10-2The K of mol/l2PdCl4Solution is added in the above-mentioned suspension containing CoAl-LDHs and is vigorously stirred, at room temperature
After stirring 12h, obtained product is filtered, is first washed with deionized 3 times, then washed 3 times with absolute ethyl alcohol, will finally obtained
Product be dried overnight in drying box in 100 DEG C, afterwards by dried catalyst in Muffle furnace, with the speed of 6 DEG C/min
Rate is warming up to 600 DEG C of roasting 5h, obtains Pd/CoAl (CP) catalyst, is denoted as catalyst C.The mass fraction of Pd is in catalyst
1.73%, through H2-O2The dispersion degree that titrimetry obtains Pd is 45.4%.
Embodiment 4
When preparing cobalt aluminum hydrotalcite using hydro-thermal method, at room temperature according to Co：Al=3:1 weighs 15.8149g CoSO42·
6H2O and 11.0025g Al2(SO4)3·18H2O is simultaneously dissolved in 200ml deionized waters, is configured to clear mixed solution A, after will
1.9812g urea is configured to clear mixed solution B.B is poured into autoclave, after solution A is added dropwise in B, while be added dropwise while
Stirring is added dropwise and is placed in baking oven 110 DEG C and keeps for 24 hours, by gained dirty solution centrifuge washing to pH=7, in 100 DEG C of dryings
Up to hydrotalcite after 12h, CoAl-LDHs is denoted as.
Then 2.0016g CoAl-LDHs are weighed to be dissolved in 200ml deionized waters, then are by 2ml substance withdrawl syndromes
5.64×10-2The Na of mol/l2PdCl4Solution is added in the above-mentioned suspension containing CoAl-LDHs and is vigorously stirred, in room temperature
After lower stirring 12h, obtained product is filtered, is first washed with deionized 3 times, then washed 3 times with absolute ethyl alcohol, obtained final
To product be dried overnight in drying box in 100 DEG C, afterwards by dried catalyst in Muffle furnace, with 4 DEG C/min's
Rate is warming up to 500 DEG C of roasting 4h, obtains Pd/CoAl (HT) catalyst, is denoted as catalyst D.The mass fraction of Pd in catalyst D
For 0.5%, through H2-O2The dispersion degree that titrimetry obtains Pd is 48.1%.
Embodiment 5
When preparing cobalt magnalium hydrotalcite using hydro-thermal method, at room temperature according to n (Co+Mg)：NAl=3:1 weighs
8.1852gCo(NO3)2·6H2O, 7.2116g Mg (NO3)2·6H2O and 7.0331g Al (NO3)3·9H2O is simultaneously dissolved in 200ml
In deionized water, be configured to clear mixed solution A, after 1.9812g urea is configured to clear mixed solution B.B is poured into
In autoclave, after solution A is added dropwise in B, stir when being added dropwise, is added dropwise and is placed in baking oven 110 DEG C and keeps for 24 hours, general
Gained dirty solution centrifuge washing, up to hydrotalcite after 100 DEG C of dry 12h, is denoted as CoMgAl-LDHs to pH=7.
Then 0.5004g CoMgAl-LDHs are weighed to be dissolved in 200ml deionized waters, then are by 7ml substance withdrawl syndromes
5.64×10-2The Na of mol/l2PdCl4Solution is added in the above-mentioned suspension containing CoMgAl-LDHs and is vigorously stirred, in room
After the lower stirring 12h of temperature, obtained product is filtered, is washed repeatedly with deionized water and ethyl alcohol, by the product finally obtained dry
It is dried overnight in dry case in 100 DEG C, dried catalyst is warming up to 600 DEG C in Muffle furnace with the rate of 4 DEG C/min afterwards
4h is roasted, Pd/CoMgAl (HT) catalyst is obtained, is denoted as catalyst E.The mass fraction of Pd is 6% in catalyst E, through H2-O2
The dispersion degree that titrimetry obtains Pd is 44.5%.
Embodiment 6
Coprecipitation prepares houghite containing cobalt：By 6.4018g NaOH and 3.1806g anhydrous Nas2CO3200ml is dissolved in go
In ionized water, poured into after stirring 20min in three-necked flask and continue to stir 1h, obtain precipitant solution；By the molar ratio of cobalt and aluminium
For 1:1 weighs 3.6485g CoCl26H respectively2O and 6.3779g AlCl3·9H2O is simultaneously dissolved in 200ml deionized waters, is filled
Cobalt salt and the mixed solution of aluminium salt are obtained after point stirring and dissolving；Then with peristaltic pump by cobalt salt and the mixed solution of aluminium salt with 6ml/
The speed of min is slowly dropped into precipitant solution and is vigorously stirred, and 60 DEG C are warming up to after being added dropwise, and continues to be stirred to react
1h stands for 24 hours after the completion of reaction, reaction solution is centrifuged, and collects sediment and washs to pH=7；Then in 100 DEG C of dry 12h,
Obtain cobalt aluminum hydrotalcite CoAl-LDHs.
Then 0.5004g CoAl-LDHs are weighed to be dissolved in 200ml deionized waters, then are by 3.5ml substance withdrawl syndromes
5.64×10-2The K of mol/l2PtCl4Solution is added in the above-mentioned suspension containing CoAl-LDHs and is vigorously stirred, at room temperature
After stirring 12h, obtained product is filtered, is first washed with deionized 3 times, then washed 3 times with absolute ethyl alcohol, will finally obtained
Product be dried overnight in drying box in 100 DEG C, afterwards by dried catalyst in Muffle furnace, with the speed of 6 DEG C/min
Rate is warming up to 600 DEG C of roasting 5h, obtains Pd/CoAl catalyst, is denoted as catalyst F.The mass fraction of Pt is in catalyst
3.46%, through H2-O2The dispersion degree that titrimetry obtains Pt is 39.2%.
Comparative example 1
1g commercial oxidation aluminium is weighed to be dissolved in 200ml deionized waters, then by 2ml substance withdrawl syndromes be 5.64 × 10- 2The Na of mol/l2PdCl4Solution addition is above-mentioned to contain Al2O3Suspension in and be vigorously stirred, after 12h is stirred at room temperature, will
Obtained product filtering, is washed repeatedly with deionized water and ethyl alcohol, by the product finally obtained in 100 DEG C of dryings in drying box
Overnight, dried catalyst is roasted into 3h in 500 DEG C in Muffle furnace afterwards, obtains Pd/Al2O3Catalyst is denoted as catalyst
G.The mass fraction of Pd is 1.2% in catalyst G, through H2-O2The dispersion degree that titrimetry obtains Pd is 23.5%.
Comparative example 2
Coprecipitation prepares catalyst：By 6.4g NaOH and 2.65g anhydrous Nas2CO3It is dissolved in 200ml deionized waters, stirs
It mixes to pour into three-necked flask after 20min and continues to stir 1h, obtain precipitant solution；It is 2 by the molar ratio of cobalt and aluminium:1 claims respectively
Take 14.8745g Co (NO3)2·6H2O and 9.3783g Al (NO3)3·9H2O and 0.1583g Na2PtCl4Be dissolved in 200ml go from
In sub- water, the mixed solution of cobalt salt, aluminium salt and precious metal salt is obtained after being sufficiently stirred dissolving；Then it is with peristaltic pump that the mixing is molten
Liquid is slowly dropped into precipitant solution and is vigorously stirred with the speed of 6ml/min, and 60 DEG C are warming up to after being added dropwise, and continues to stir
Reaction 1h is mixed, is stood for 24 hours after the completion of reaction, reaction solution is centrifuged, sediment is collected and washs to pH=7；Then it is dry at 100 DEG C
The product finally obtained is dried overnight, afterwards by dried catalyst in Muffle furnace by dry 12h in drying box in 100 DEG C
In, 550 DEG C of roasting 3h are warming up to the rate of 5 DEG C/min, Pt/CoAl catalyst is obtained, is denoted as catalyst H.In catalyst H
The mass fraction of Pt is 3.25%, through H2-O2The dispersion degree that titrimetry obtains Pt is 31.6%.
Experimental example
1. the desulfurization effect test of catalyst
The activity rating of catalyst prepared by above-mentioned case is produced by Beijing Xin Hangdun petrochemical industry Science and Technology Ltd.
(MRT-6113,500 DEG C of system design pressure, system design temperature are carried out on microscale experiment reaction unit：8MPa, in reactor
Footpath 10mm.
N-heptane solution using thiophene or 4,6- dimethyl Dibenzothiophenes (4,6-DMDBT) content as 3wt% is model
Raw materials of compound.Rhohene desulfiirization reacts：2g catalyst is packed into hydrodesulfurization unit, first at 300 DEG C, with hydrogen (50ml/
Min) to oxidized catalyst presoma reductase 12 h.Switching reaction, reaction condition are after the completion of reduction：Normal pressure, 350 DEG C, hydrogen
Flow is 150ml min-1.Then pure hydrogen passes through the chemical industry saturator containing organic sulfur at 18 DEG C of constant temperature.After reaction, adopt
Analysis test is carried out with GC.
The thiophene of 1 catalyst of table and the evaluation index of 6- dimethyl Dibenzothiophene Hydrobon catalysts
Table 1 is the Hydrobon catalyst of the catalyst prepared in embodiment 1-6 and comparative example 1-2 using the method for the present invention
Evaluation index.
As it can be seen from table 1 Hydrobon catalyst (sample A-F) of the present invention can reach in differential reactor
To higher conversion ratio, the wherein thiophene conversion ratio of sample B is reachable up to 96.8%, 4,6- dimethyl Dibenzothiophene conversion ratio
86.9%, conversion ratio illustrates that catalyst prepared by the present invention has higher hydrogenation apparently higher than other samples and business sample
Desulfurization (especially macromolecular organic sulfur compound) activity.In addition in comparative example 2, noble metal is directly added into houghite,
Obtained catalyst effect is not so good as the catalyst B of equal bullion content.After being tested when 40h is small, catalyst B still has
There is higher conversion ratio, the conversion ratio of 4, the 6- dimethyl Dibenzothiophenes of sample A-F has reduction, but the range of decrease is little, and
What thiophene conversion ratio reduced in comparative example 1 and 2 is more.Illustrating the scheme of the patent has good effect.
Obviously, the above embodiments are merely examples for clarifying the description, and is not intended to limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation thus extended out or
Among changing still in the protection domain of the invention.
Claims (12)
1. a kind of noble metal hydrogenation desulphurization catalyst, which is characterized in that including carrier and noble metal active component, the carrier
Presoma is houghite containing cobalt, and the noble metal active component is distributed in the surface of houghite containing cobalt with oxidation states.
2. noble metal hydrogenation desulphurization catalyst according to claim 1, which is characterized in that the houghite containing cobalt is cobalt
Aluminium houghite or cobalt magnesia-alumina hydrotalcite.
3. noble metal hydrogenation desulphurization catalyst according to claim 1 or 2, which is characterized in that the noble metal active group
It is divided into platinum or palladium.
4. noble metal hydrogenation desulphurization catalyst according to claim 3, which is characterized in that the noble metal active component is pressed
According to the quality meter of its simple substance, the 0.5-6% of noble metal hydrogenation desulphurization catalyst is accounted for.
5. a kind of preparation method of any one of claim 1-4 noble metal hydrogenation desulphurization catalysts, which is characterized in that including
Following steps：
(1) using conventional method, by aging, centrifuge, be dried to obtain houghite containing cobalt；
(2) cobalt houghite will be contained to be dispersed in water, and will obtain the slurries of houghite containing cobalt, the salting liquid of noble metal will be mixed with it
It closes, stirs 6-18h, stand, filter, wash, it is dry；
(3) step (2) products obtained therefrom is roasted, calcination temperature is 400-600 DEG C, roasting time 2-4h, is obtained described expensive
Metal hydrogenation desulphurization catalyst.
6. the preparation method of noble metal hydrogenation desulphurization catalyst according to claim 5, which is characterized in that the noble metal
Salting liquid for chloroplatinate solution or chloropalladate solution, preferred chloroplatinate solution is Na2PtCl4Or K2PtCl4It is molten
Liquid, preferred chloropalladate solution are Na2PdCl4Or K2PdCl4Solution.
7. the preparation method of noble metal hydrogenation desulphurization catalyst according to claim 5, which is characterized in that the noble metal
Salting liquid concentration be 0.05-0.15mol/l.
8. the preparation method of noble metal hydrogenation desulphurization catalyst according to claim 5, which is characterized in that calcination steps
Heating rate is 3-6 DEG C/min.
9. the preparation method of noble metal hydrogenation desulphurization catalyst according to claim 5, which is characterized in that using co-precipitation
Method or hydro-thermal method prepare houghite containing cobalt.
10. described in a kind of claim 1-4 any one of them noble metal hydrogenation desulphurization catalysts or claim any one of 5-9
In the organic sulfur compound reaction of the noble metal hydrogenation desulphurization catalyst that preparation method is prepared macromolecular in feedstock oil is removed
Application.
11. the organic sulfide of noble metal hydrogenation desulphurization catalyst according to claim 10 macromolecular in feedstock oil is removed
Application in object reaction, which is characterized in that the macromolecular organic sulfur compound is thiophene, benzothiophene, dibenzothiophenes, 2,5-
Thioxene or 4,6- dimethyl Dibenzothiophenes.
12. according to 10 or 11 any one of them noble metal hydrogenation desulphurization catalyst of claim in feedstock oil is removed macromolecular
Application in organic sulfur compound reaction, which is characterized in that the noble metal hydrogenation desulphurization catalyst is gone back in advance before use
Original place is managed, and hydrodesulfurization reaction condition is:Normal pressure, 280-400 DEG C, hydrogen to oil volume ratio 100-500, liquid hourly space velocity (LHSV) 0.5-
2.5h-1, when reaction time 8-24 is small.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109158120A (en) * | 2018-08-01 | 2019-01-08 | 东北大学 | A kind of CO based on absorption humidification2Hydrogenation catalyst and preparation method thereof |
| CN110433826A (en) * | 2019-07-30 | 2019-11-12 | 北京氦舶科技有限责任公司 | A kind of monatomic Au catalyst and its preparation method and application |
| CN110763773A (en) * | 2018-07-27 | 2020-02-07 | 中国石油化工股份有限公司 | Analysis method of biomarker compounds in crude oil asphaltenes |
| CN113368868A (en) * | 2021-07-13 | 2021-09-10 | 北京化工大学 | Supported sub-nano noble metal catalyst and preparation method thereof |
| CN113713800A (en) * | 2021-09-15 | 2021-11-30 | 中国石油化工股份有限公司 | High-temperature flue gas desulfurizer and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102822097A (en) * | 2010-03-09 | 2012-12-12 | 马克斯-普朗克科学促进学会 | Palladium-modified hydrotalcites and their use as catalyst precursors |
| CN103601255A (en) * | 2013-10-30 | 2014-02-26 | 中国科学院化学研究所 | Three-dimensional micro/nano hierarchically-structured cobalt-aluminium hydrotalcite material, and preparation method and applications thereof |
| CN103977794A (en) * | 2014-04-29 | 2014-08-13 | 北京化工大学 | Supported noble metal catalyst with three-dimensional structure and preparation method and application thereof |
| CN106179333A (en) * | 2016-07-11 | 2016-12-07 | 山东师范大学 | A kind of method of palladium magnesia-alumina hydrotalcite catalyzed Sonogashira cross-coupling reaction |
-
2017
- 2017-11-23 CN CN201711182047.4A patent/CN108067252A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102822097A (en) * | 2010-03-09 | 2012-12-12 | 马克斯-普朗克科学促进学会 | Palladium-modified hydrotalcites and their use as catalyst precursors |
| CN103601255A (en) * | 2013-10-30 | 2014-02-26 | 中国科学院化学研究所 | Three-dimensional micro/nano hierarchically-structured cobalt-aluminium hydrotalcite material, and preparation method and applications thereof |
| CN103977794A (en) * | 2014-04-29 | 2014-08-13 | 北京化工大学 | Supported noble metal catalyst with three-dimensional structure and preparation method and application thereof |
| CN106179333A (en) * | 2016-07-11 | 2016-12-07 | 山东师范大学 | A kind of method of palladium magnesia-alumina hydrotalcite catalyzed Sonogashira cross-coupling reaction |
Non-Patent Citations (4)
| Title |
|---|
| S. ALBERTAZZI ET AL.: "New Pd/Pt on Mg/Al basic mixed oxides for the hydrogenation and hydrogenolysis of naphthalene", 《JOURNAL OF CATALYSIS》 * |
| YOSHIO ONO ET AL.: "《固体碱催化》", 31 May 2013 * |
| 何杰: "《工业催化》", 31 August 2014, 中国矿业大学出版社 * |
| 杨晓东: "载体对Pd和Pt催化剂加氢脱硫反应性能的影响", 《化学反应工程与工艺》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110763773A (en) * | 2018-07-27 | 2020-02-07 | 中国石油化工股份有限公司 | Analysis method of biomarker compounds in crude oil asphaltenes |
| CN110763773B (en) * | 2018-07-27 | 2022-12-27 | 中国石油化工股份有限公司 | Analysis method of biomarker compounds in crude oil asphaltenes |
| CN109158120A (en) * | 2018-08-01 | 2019-01-08 | 东北大学 | A kind of CO based on absorption humidification2Hydrogenation catalyst and preparation method thereof |
| CN109158120B (en) * | 2018-08-01 | 2020-04-14 | 东北大学 | CO based on adsorption enhancement effect2Hydrogenation catalyst and preparation method thereof |
| CN110433826A (en) * | 2019-07-30 | 2019-11-12 | 北京氦舶科技有限责任公司 | A kind of monatomic Au catalyst and its preparation method and application |
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